JPWO2015068739A1 - Automotive interior parts - Google Patents

Abstract

A predetermined acetone-insoluble component (A) and a predetermined acetone-soluble component (B). An automotive interior part comprising a thermoplastic resin composition of 5 to 18% by mass relative to 100% by mass of B) in total.

Description

  The present invention relates to automobile interior parts.

  Acrylonitrile-butadiene-styrene copolymer (ABS resin) is a well-balanced resin with excellent fluidity, impact resistance, chemical resistance, and surface appearance, so it can be used for automotive parts, OA equipment, and home appliances. It has been used in various fields such as toy casings.

  In recent years, materials having high aesthetics in addition to performance such as impact resistance have been demanded in addition to performance such as impact resistance, instead of painting household appliances such as TV casings, OA equipment, and toys. . As such a material, a resin in which an alloy of ABS resin and PMMA is colored in jet black has been proposed (see, for example, Patent Document 1).

  In addition, when an automobile interior part or the like is not to be painted, a material having high heat resistance is required in addition to design characteristics such as deep jetness and scratch resistance. In this respect, the alloy described in Patent Document 1 can obtain jet blackness and scratch resistance, but cannot obtain high heat resistance, so that it is difficult to develop it into automobile interior parts.

  Then, the heat resistant transparent resin composition excellent in heat resistance, impact resistance, and transparency for automobile interior parts has been proposed (see, for example, Patent Document 2).

JP 2009-0679970 A JP 2005-298776 A

  However, when a jet black molded product is produced using the heat-resistant transparent resin composition described in Patent Document 2, white haze (unevenness of color tone or cloudiness) and silver are formed on the molded product surface due to changes in molding temperature and molding pressure. There is a problem that (silver strip) occurs. Further, regarding the particle diameter of the methacrylic acid ester resin that is a factor of silver (scratch resistance) and the rubber-modified thermoplastic resin that is a factor of white haze, in view of the description of the examples and comparative examples of Reference 2 There is no description of a resin composition that solves both white haze and silver due to changes in molding temperature and pressure.

  Therefore, the present invention has been made in view of the above problems, and has a jet-blackness, scratch resistance, heat resistance, and impact resistance, and has a stable and beautiful appearance without silver and white haze. The purpose is to provide parts.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a predetermined thermoplastic resin composition, and have completed the present invention.

That is, the present invention is as follows.
[1]
Including acetone-insoluble matter (A) and acetone-soluble matter (B),
The content of the acetone insoluble component (A) is 5 to 18% by mass with respect to 100% by mass in total of the acetone insoluble component (A) and the acetone soluble component (B),
The acetone-insoluble component (A) contains one or more resins having different structural units, and the constituent units of all the resins contained in the acetone-insoluble component (A) have at least a mass average particle size of 0.00. 1 to 0.35 μm rubber component units, aromatic vinyl monomer units, and unsaturated nitrile monomer units are included,
The acetone insoluble matter (A) includes a graft copolymer in which at least the unsaturated nitrile monomer unit is grafted to the rubber component unit,
The content of the unsaturated nitrile monomer unit contained in the graft copolymer is 15 to 28% by mass with respect to 100% by mass of all grafted structural units,
The acetone-soluble component (B) includes one or more resins having different structural units, and the structural units of all resins included in the acetone-soluble component (B) include at least aromatic vinyl unit. A monomer unit, an unsaturated nitrile monomer unit, a methacrylate ester monomer unit, and a maleimide monomer unit,
It consists of a thermoplastic resin composition whose content of the said methacrylic acid ester monomer unit is 45-60 mass% with respect to 100 mass% of all resin structural units contained in the said acetone soluble part (B). ,
Automotive interior parts.
[2]
The automotive interior part according to [1] above, wherein the thermoplastic resin composition has a Vicat softening point in accordance with ISO 306 of 105 to 120 ° C.
[3]
The automobile interior part according to [1] or [2] above, wherein the content of the maleimide monomer unit is 5 to 13% by mass with respect to 100% by mass of the thermoplastic resin composition.
[4]
The automobile interior part according to any one of [1] to [3], wherein the rubber component unit includes a diene rubber unit.
[5]
Any one of [1] to [4] above, wherein the content of the rubber unit is 30 to 60% by mass with respect to 100% by mass of the structural units of all resins contained in the acetone insoluble matter (A). The automobile interior part described in the item.

  According to the present invention, it is possible to provide an automobile interior part having jet blackness, scratch resistance, heat resistance, and impact resistance and having a stable and beautiful appearance without silver and white haze.

  DESCRIPTION OF EMBODIMENTS Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to this, and various modifications can be made without departing from the gist thereof. Is possible. The “monomer” means a polymerizable molecule before constituting the resin, and the “monomer unit” or “unit” means a unit constituting the resin corresponding to a predetermined monomer. Say.

[Automobile interior parts]
The automobile interior part according to this embodiment is
Including acetone-insoluble matter (A) and acetone-soluble matter (B),
The content of the acetone insoluble component (A) is 5 to 18% by mass with respect to 100% by mass in total of the acetone insoluble component (A) and the acetone soluble component (B),
The acetone-insoluble component (A) contains one or more resins having different structural units, and the constituent units of all the resins contained in the acetone-insoluble component (A) have at least a mass average particle size of 0.00. 1 to 0.35 μm rubber component units, aromatic vinyl monomer units, and unsaturated nitrile monomer units are included,
The acetone insoluble matter (A) includes a graft copolymer in which at least the unsaturated nitrile monomer unit is grafted to the rubber component unit,
The content of the unsaturated nitrile monomer unit contained in the graft copolymer is 15 to 28% by mass with respect to 100% by mass of all grafted structural units,
The acetone-soluble component (B) includes one or more resins having different structural units, and the structural units of all resins included in the acetone-soluble component (B) include at least aromatic vinyl unit. A monomer unit, an unsaturated nitrile monomer unit, a methacrylate ester monomer unit, and a maleimide monomer unit,
It consists of a thermoplastic resin composition whose content of the said methacrylic acid ester monomer unit is 45-60 mass% with respect to 100 mass% of all resin structural units contained in the said acetone soluble part (B). .

[Acetone insoluble matter (A)]
The thermoplastic resin composition according to this embodiment includes an acetone insoluble matter (A). The acetone-insoluble component (A) includes one or more resins having different structural units, and the structural units of all the resins included in the acetone-insoluble component (A) include at least a mass average particle size of 0.1 to 0.1. A 0.35 μm rubber component unit, an aromatic vinyl monomer unit, and an unsaturated nitrile monomer unit are included.

  Here, “acetone insoluble matter (A)” refers to a component that is not dissolved in acetone when the thermoplastic resin composition according to the present embodiment is dissolved in acetone. The acetone insoluble matter (A) can be specified by the method described in Examples.

  The “structural unit of all resins contained in acetone-insoluble matter (A)” refers to all constituent units constituting the resin when the resin contained in acetone-insoluble matter (A) is one kind. In the case where two or more kinds of resins are contained in the acetone insoluble matter (A), it means all the structural units constituting each resin. That is, the resin contained in the acetone-insoluble component (A) is not particularly limited. For example, a resin containing a rubber component unit, a resin containing an aromatic vinyl monomer unit, and an unsaturated nitrile monomer unit may be used. A combination of a resin containing a rubber component unit and an aromatic vinyl monomer unit and a resin containing an unsaturated nitrile monomer unit; a resin containing a rubber component unit and an aromatic vinyl monomer A combination of a resin containing a unit and an unsaturated nitrile monomer unit; a combination of a resin containing a rubber component unit and a resin containing an unsaturated nitrile monomer unit and a resin containing an aromatic vinyl monomer unit; rubber Examples thereof include a resin alone containing a component unit, an aromatic vinyl monomer unit, and an unsaturated nitrile monomer unit.

  The rubber component unit is not particularly limited. For example, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, polyisoprene, polychloroprene, styrene-butadiene block copolymer (Conjugated) diene rubber unit comprising at least one selected from the group consisting of a polymer, a styrene-isoprene block copolymer, an ethylene-propylene-diene terpolymer, and the like; an acrylic system comprising polybutyl acrylate, etc. Examples thereof include rubber units; ethylene-propylene rubber units; silicon rubber units; silicone-acrylic composite rubber units; and rubber units composed of hydrogenated products thereof. Among these, (conjugated) diene rubber units are preferable, and polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, and styrene-butadiene block copolymer are more preferable. By using a (conjugated) diene rubber unit, impact resistance tends to be further improved. A rubber component unit may be used individually by 1 type, or may use 2 or more types together.

  The glass transition temperature of the polymer contained in the rubber component unit is preferably 0 ° C. or lower, more preferably −50 ° C. or lower, and further preferably −70 ° C. or lower. The glass transition temperature can be measured by DSC according to a conventional method.

  The mass average particle diameter of the rubber component unit is 0.1 to 0.35 μm, preferably 0.12 to 0.33 μm, and more preferably 0.15 to 0.3 μm. When the mass average particle diameter is 0.1 μm or more, impact resistance is further improved. Moreover, by being 0.35 micrometer or less, design properties, such as jet blackness, improve more, and a white haze is suppressed more. A mass average particle diameter can be measured by the method as described in an Example. The “mass average particle diameter of the rubber component unit” is the size of the rubber component unit, and in the case of a graft copolymer, the graft copolymer portion is excluded.

  The content of the rubber component unit is preferably 30 to 60% by mass, more preferably 35 to 60% by mass, with respect to 100% by mass of the constituent units of all resins contained in the acetone insoluble matter (A). More preferably, it is 40-55 mass%. When the content of the rubber component unit is within the above range, the compatibility with the acetone-soluble component (impact etc.) is excellent. The rubber unit content can be measured by the method described in Examples.

  Although it does not specifically limit as an aromatic vinyl monomer unit, For example, a styrene unit, (alpha) -methylstyrene unit, o-methylstyrene unit, p-methylstyrene unit, o-ethylstyrene unit, p-ethylstyrene unit, Examples thereof include a pt-butylstyrene unit and a vinylnaphthalene unit. Of these, styrene units and α-methylstyrene units are preferred. An aromatic vinyl monomer unit may be used individually by 1 type, or may use 2 or more types together.

  Although it does not specifically limit as an unsaturated nitrile monomer unit, For example, an acrylonitrile unit, a methacrylonitrile unit, an ethacrylonitrile unit, etc. are mentioned. Of these, acrylonitrile units are preferred. An unsaturated nitrile monomer unit may be used individually by 1 type, or may use 2 or more types together.

  Other monomer units that can be copolymerized are not particularly limited, and examples thereof include unsaturated carboxylic acid alkyl ester monomer units; N units such as maleic anhydride units, N-phenylmaleimide units, and N-methylmaleimide units. -Substituted maleimide monomer units; glycidyl group-containing monomer units such as glycidyl methacrylate units. Other copolymerizable monomer units may be used alone or in combination of two or more.

  The unsaturated carboxylic acid alkyl ester monomer unit is not particularly limited. For example, an acrylic acid ester compound unit such as a butyl acrylate unit, an ethyl acrylate unit, a methyl acrylate unit, or a methyl methacrylate unit, and a methacrylic acid ester compound unit; Examples thereof include acrylic acid units such as acid units and methacrylic acid units. Although it does not specifically limit as a copolymerization component in this case, For example, aromatic vinyl-type monomers, such as styrene and (alpha) -methylstyrene; Methyl acrylate, (meth) acrylic acid ethyl, (meth) acrylic acid n- Propyl, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acryl Unsaturated carboxylic acid alkyl esters such as 3-hydroxypropyl acid, 2,3,4,5,6-pentahydroxyhexyl (meth) acrylate, and 2,3,4,5-tetrahydroxypentyl (meth) acrylate Monomer. These may be used alone or in combination of two or more.

(Graft copolymer)
The acetone insoluble component (A) includes a graft copolymer in which at least an unsaturated nitrile monomer unit is grafted to a rubber component unit. The acetone-insoluble component (A) includes a graft copolymer in which at least an aromatic vinyl monomer unit is grafted to a rubber component unit, and an aromatic vinyl monomer unit and an unsaturated nitrile monomer to a rubber component unit. It is preferable to include a graft copolymer in which the units are grafted. The polymer grafted to the rubber component unit can also contain other monomer units copolymerizable with the aromatic vinyl monomer and the unsaturated nitrile monomer. By including such a graft copolymer, the compatibility with the acetone-soluble component (matrix) is strong and the impact property tends to be excellent.

  The polymer to be grafted is not particularly limited. For example, acrylonitrile-styrene copolymer, acrylonitrile-α-methylstyrene copolymer, acrylonitrile-styrene-butyl acrylate copolymer, acrylonitrile-styrene-methyl methacrylate copolymer And acrylonitrile-styrene-N-phenylmaleimide copolymer and the like. Of these, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butyl acrylate copolymer, and acrylonitrile-styrene-methyl methacrylate copolymer are preferable.

  The content of the unsaturated nitrile monomer unit contained in the graft copolymer is 15 to 28% by mass, preferably 17 to 27% by mass, based on 100% by mass of all grafted structural units, More preferably, it is 18-25 mass%. When the content of the unsaturated nitrile monomer unit is 15% by mass or more, impact resistance tends to be further improved. Moreover, when the content of the unsaturated nitrile monomer unit is 28% by mass or less, design properties such as jetness tend to be further improved. The content of the unsaturated nitrile monomer unit can be measured by the method described in the examples.

  Although it does not specifically limit as a manufacturing method of a graft copolymer, For example, methods, such as emulsion polymerization, suspension polymerization, block polymerization, solution polymerization, and the combination of these polymerization methods, are mentioned. Specifically, there is an emulsion graft polymerization method in which a copolymer is graft-polymerized to latex of a rubber component produced by emulsion polymerization. It is possible to adopt any of continuous, batch, and semi-batch methods.

  The ratio (graft ratio) of the copolymer grafted to the rubber component unit produced in the production process of the graft copolymer is preferably 10 to 200% by mass, more preferably 100% by mass of the rubber component unit. It is 20-170 mass%, More preferably, it is 30-100 mass%. The graft ratio can be defined by the mass ratio of the copolymer (graft component) grafted to the rubber component unit with respect to 100% by mass of the graft copolymer. The graft rate can be measured by the method described in the examples.

  The content of the graft copolymer is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and further preferably 80 to 100% by mass with respect to 100% by mass of the acetone insoluble matter (A). %. When the content of the graft copolymer is within the above range, the impact property tends to be superior.

  The content of the acetone-insoluble component (A) is 5 to 18% by mass, preferably 7 to 18% by mass, with respect to 100% by mass in total of the acetone-insoluble component (A) and the acetone-soluble component (B). Yes, more preferably 10 to 17% by mass. When the content of the acetone insoluble matter (A) is 5% by mass or more, the impact resistance and the mold releasability are improved. Moreover, scratch resistance and heat resistance improve more because content of an acetone insoluble content (A) is 18 mass% or less. Content of acetone insoluble matter (A) can be measured by the method as described in an Example.

[Acetone soluble matter (B)]
The thermoplastic resin composition according to this embodiment includes an acetone-soluble component (B). The acetone-soluble component (B) contains one or more resins having different structural units, and the constituent units of all resins contained in the acetone-soluble component (B) include at least an aromatic vinyl monomer. Units, unsaturated nitrile monomer units, methacrylate ester monomer units, and maleimide monomer units are included.

  Here, the “acetone soluble component (B)” refers to a component dissolved in acetone when the thermoplastic resin composition according to the present embodiment is dissolved in acetone. The acetone-soluble component (B) can be specified by the method described in Examples.

  In addition, the “structural unit of all resins contained in the acetone-soluble component (B)” refers to all constituent units constituting the resin when the resin contained in the acetone-soluble component (B) is one kind. In the case where two or more kinds of resins are contained in the acetone-soluble component (B), it means all the structural units constituting each resin. That is, the resin contained in the acetone-soluble component (B) is not particularly limited. For example, a resin containing an aromatic vinyl monomer unit, a resin containing an unsaturated nitrile monomer unit, and a methacrylate ester A combination of a resin containing a monomer unit and a resin containing a maleimide monomer unit; a resin containing an aromatic vinyl monomer unit and an unsaturated nitrile monomer unit, and a methacrylic acid ester monomer unit A resin comprising a maleimide monomer unit; a resin comprising an aromatic vinyl monomer unit and a methacrylate ester monomer unit; a resin comprising an unsaturated nitrile monomer unit; A resin containing an aromatic monomer unit; a resin containing an aromatic vinyl monomer unit and a maleimide monomer unit; a resin containing an unsaturated nitrile monomer unit; A combination of a resin containing a sulfonate monomer unit; a resin containing an aromatic vinyl monomer unit, a resin containing an unsaturated nitrile monomer unit and a methacrylate ester monomer unit, and a maleimide monomer A resin containing an aromatic vinyl monomer unit, a resin containing an unsaturated nitrile monomer unit and a maleimide monomer unit, and a resin containing a methacrylic acid ester monomer unit A combination of a resin containing an aromatic vinyl monomer unit, an unsaturated nitrile monomer unit, and a methacrylic acid ester monomer unit, and a resin containing a maleimide monomer unit; Combination of a resin containing a monomer unit, an unsaturated nitrile monomer unit, and a maleimide monomer unit and a resin containing a methacrylic acid ester monomer unit; aromatic vinyl A combination of a resin containing a monomer unit, a methacrylic acid ester monomer unit, and a maleimide monomer unit and a resin containing an unsaturated nitrile monomer unit; a resin containing an aromatic vinyl monomer unit; Combination with unsaturated nitrile monomer unit, methacrylate monomer unit, and resin containing maleimide monomer unit; aromatic vinyl monomer unit, unsaturated nitrile monomer unit, methacrylate ester unit Examples thereof include a resin unit containing a monomer unit and a maleimide monomer unit.

  The resin contained in the acetone-soluble component (B) is preferably a mixture of at least two types of copolymers. Two or more types of copolymers are preferably compatible. Whether two or more kinds of copolymers are compatible can be confirmed by determining Tg to be one.

  Although it does not specifically limit as an aromatic vinyl monomer unit, For example, a styrene unit, (alpha) -methylstyrene unit, o-methylstyrene unit, p-methylstyrene unit, o-ethylstyrene unit, p-ethylstyrene unit, Examples thereof include a pt-butylstyrene unit and a vinylnaphthalene unit. Of these, styrene units and α-methylstyrene units are preferred. An aromatic vinyl monomer unit may be used individually by 1 type, or may use 2 or more types together.

  Although it does not specifically limit as an unsaturated nitrile monomer unit, For example, an acrylonitrile unit, a methacrylonitrile unit, an ethacrylonitrile unit, etc. are mentioned. Of these, acrylonitrile units are preferred. An unsaturated nitrile monomer unit may be used individually by 1 type, or may use 2 or more types together.

  The methacrylic acid ester monomer unit is not particularly limited, and examples thereof include butyl methacrylate unit, ethyl methacrylate unit, methyl methacrylate unit, propyl methacrylate unit, isopropyl methacrylate unit, cyclohexyl methacrylate unit, and phenyl methacrylate. Examples include units, methacrylic acid (2-ethylhexyl) units, methacrylic acid (t-butylcyclohexyl) units, benzyl methacrylate units, and methacrylic acid (2,2,2-trifluoroethyl) units. Of these, methyl methacrylate units are preferred. A methacrylic acid ester monomer unit may be used individually by 1 type, or may use 2 or more types together.

  The content of the methacrylic acid ester monomer unit is 45 to 60% by mass, preferably 52 to 58% by mass, based on 100% by mass of the structural units of all resins contained in the acetone-soluble component (B). Yes, more preferably 53 to 57% by mass. When the content of the methacrylic acid ester monomer unit is 45% by mass or more, pencil hardness and scratch resistance are further improved. Moreover, when the content of the methacrylic acid ester monomer unit is 60% by mass or less, impact resistance and releasability during molding are further improved. The content of the methacrylic acid ester monomer unit can be measured by the method described in Examples.

  Although it does not specifically limit as a maleimide monomer unit, For example, a maleimide unit, N-methylmaleimide unit, N-ethylmaleimide unit, N-cyclohexylmaleimide unit, N-phenylmaleimide unit, N- (o-chlorophenyl) maleimide Units, N- (m-chlorophenyl) maleimide units, N- (p-chlorophenyl) maleimide units, and the like. Of these, N-cyclohexylmaleimide units and N-phenylmaleimide units are preferable. The maleimide monomer units may be used alone or in combination of two or more.

  The content of the maleimide monomer unit is preferably 2.5 to 15% by mass, more preferably 5.0% with respect to 100% by mass of the structural units of all resins contained in the acetone-soluble component (B). It is -12.5 mass%, More preferably, it is 7.5-10 mass%. When the content of the maleimide monomer unit is 2.5% by mass or more, the heat resistance tends to be further improved. Moreover, when content of a maleimide monomer unit is 15 mass% or less, there exists a tendency which a moldability improves more, a white haze is suppressed more, and an external appearance improves more.

  Examples of other copolymerizable monomer units include acrylate monomer units. The acrylate monomer unit is not particularly limited. For example, butyl acrylate unit, ethyl acrylate unit, methyl acrylate unit, propyl acrylate unit, isopropyl acrylate unit, cyclohexyl acrylate unit, phenyl acrylate unit Examples include units, acrylic acid (2-ethylhexyl) units, acrylic acid (t-butylcyclohexyl) units, benzyl acrylate units, and acrylic acid (2,2,2-trifluoroethyl).

(Vinyl copolymer and methacrylic copolymer)
The combination of resins contained in the acetone-soluble component (B) is not particularly limited. For example, aromatic vinyl monomer units, unsaturated nitrile monomer units, and other units copolymerizable with these units. Combinations of vinyl copolymers composed of monomer units, methacrylate monomer units, maleimide monomer units, and other methacrylic copolymers composed of other monomer units copolymerizable therewith preferable. The resin contained in the acetone-soluble component (B) may be used alone or in combination of two or more.

  The content of the unsaturated nitrile monomer unit in the vinyl copolymer contained in the acetone-soluble component (B) is preferably 15 to 28% by mass, more preferably 17 to 27% by mass, More preferably, it is 18-25 mass%. When the content of the unsaturated nitrile monomer unit is 15% by mass or more, impact resistance tends to be further improved. Moreover, because the content of the unsaturated nitrile monomer unit is 28% by mass or less, compatibility with the methacrylic copolymer contained in the acetone-soluble component (B), design properties such as jet blackness, and the like are further improved. It tends to improve.

  The vinyl copolymer contained in the acetone-soluble component (B) is preferably produced by radical polymerization. Although it does not specifically limit as a manufacturing method of a vinyl type copolymer, For example, a block polymerization method, a solution polymerization method, a suspension polymerization method, a block suspension polymerization method, an emulsion polymerization method etc. are mentioned. Of these, bulk polymerization, solution polymerization, and bulk suspension polymerization are preferred.

  The weight average molecular weight of the vinyl copolymer is preferably 60,000 to 300,000, more preferably 80,000 to 200,000, still more preferably 80,000 to 150,000. When the weight average molecular weight of the vinyl copolymer is within the above range, it tends to be more excellent in impact properties and moldability.

  The content of the methacrylic acid ester monomer unit in the methacrylic copolymer contained in the acetone-soluble component (B) is preferably 75 to 97% by mass, more preferably 75 to 95% by mass, More preferably, it is 80-95 mass%. When the content of the methacrylic acid ester monomer unit is 75% by mass or more, the pencil hardness and jetness tend to be further improved. Moreover, it exists in the tendency which heat resistance improves more because content of a methacrylic acid ester monomer unit is 97 mass% or less.

  The content of the maleimide monomer unit in the methacrylic copolymer contained in the acetone-soluble component (B) is preferably 3 to 25% by mass, more preferably 5 to 25% by mass, Preferably it is 5-20 mass%. When the content of the maleimide monomer unit is 3% by mass or more, the heat resistance tends to be further improved. Moreover, when the content of the maleimide monomer unit is 25% by mass or less, the compatibility with the vinyl copolymer contained in the acetone-soluble component (B) and the appearance such as white haze are further improved. Tend to.

  Although it does not specifically limit as a manufacturing method of the methacrylic copolymer contained in acetone soluble part (B), For example, block polymerization method, solution polymerization method, suspension polymerization method, precipitation polymerization method, emulsion polymerization method, etc. Is mentioned. Of these, bulk polymerization, solution polymerization, and suspension polymerization are preferred.

  The weight average molecular weight of the methacrylic copolymer is preferably 60,000 to 300,000, more preferably 60,000 to 250,000, and further preferably 70,000 to 230,000. When the weight average molecular weight of the methacrylic copolymer is within the above range, it tends to be more excellent in impact properties and moldability.

  The weight average molecular weights of the vinyl copolymer and the methacrylic copolymer can be measured by the method described in Examples.

(Characteristics of automotive interior parts)
In the automotive interior part of the present embodiment, the Vicat softening point based on ISO 306 is preferably 105 to 120 ° C, more preferably 107 to 119 ° C, and further preferably 110 to 119 ° C. When the Vicat softening point is 105 ° C. or higher, the heat resistance necessary for automobile interior parts tends to be satisfied. Moreover, when Vicat softening point is 120 degrees C or less, designability, such as a moldability and jet black, improves more, white haze is suppressed more, and there exists a tendency for an external appearance property to improve more. The Vicat softening point can be measured by the method described in Examples.

  The method for adjusting the Vicat softening point to 105 to 120 ° C. is not particularly limited. For example, a resin containing a maleimide monomer unit having a glass transition point of 150 ° C. or higher in an acetone-soluble component (B). The method of adding is mentioned. The glass transition point of the resin containing a maleimide monomer unit is preferably 150 ° C. or higher, more preferably 165 ° C. or higher, and further preferably 170 ° C. or higher. The upper limit of the glass transition point is not particularly limited, but is preferably 220 ° C. or lower. Since the glass transition point is 150 ° C. or higher, the amount of the resin containing the maleimide monomer unit necessary for adjusting the Vicat softening point to a specific range can be reduced, so that the maleimide monomer unit is included. There exists a tendency which can suppress the deterioration of compatibility with the acetone insoluble matter (A) resulting from the excessive use amount of resin, and the fall of impact resistance more.

  The content of the maleimide monomer unit is preferably 5 to 13% by mass and more preferably 7 to 10% by mass with respect to 100% by mass of the thermoplastic resin composition. When the content of the maleimide monomer unit is 5% by mass or more, the heat resistance tends to be further improved. Moreover, when content of a maleimide-type monomer unit is 13 mass% or less, there exists a tendency which a moldability improves more, a white haze is suppressed more, and an external appearance improves more.

  In the automotive interior part of the present embodiment, the lightness (L *) based on JIS Z8722 is preferably 6.5 or less, more preferably 6.2 or less, and even more preferably 6.1 or less. The smaller the lightness (L *) is, the higher the jetness is, and when the lightness (L *) is within the above range, the jetness tends to be further improved. The lightness (L *) can be measured by the method described in the examples.

  Although it does not specifically limit as a method of adjusting lightness (L *) to 6.5 or less, For example, the method of raising the transparency of resin contained in a thermoplastic resin composition is mentioned. Methods for increasing the transparency of the thermoplastic resin composition include a method in which a vinyl copolymer and a methacrylic copolymer that can be contained in the acetone-soluble component (B) are compatible, and / or an acetone-insoluble component (A The method of adjusting the mass average particle diameter of the rubber component unit in the specific range is given.

  In order to make the vinyl copolymer and the methacrylic copolymer that can be contained in the acetone-soluble component (B) compatible, the ratio of the unsaturated nitrile monomer unit in the vinyl copolymer and the methacrylic copolymer The method of adjusting the ratio of the maleimide-type monomer in a polymer is mentioned.

  Further, the smaller the mass average particle diameter of the rubber component unit, the higher the transparency of the thermoplastic resin composition, but the lower the impact resistance. Therefore, in this embodiment, the target brightness is achieved by adjusting the mass average particle diameter of the rubber component unit to a predetermined range.

  In the automobile interior part of the present embodiment, the pencil hardness according to JIS K5400 is preferably HB or more, more preferably F or more. When the pencil hardness is equal to or higher than HB, the scratch resistance when the molded body is used in an automobile room tends to be further improved. The pencil hardness can be measured by the method described in the examples.

  In this embodiment, the method for adjusting the pencil hardness to HB or higher is not particularly limited. For example, the method for adjusting the content of methacrylic acid ester monomer units that can be contained in the acetone-soluble component (B). Is mentioned.

  When the content of the methacrylic acid ester monomer unit that can be contained in the acetone-soluble component (B) is increased, the pencil hardness tends to increase, but since the content of the maleimide monomer unit decreases, the heat resistance Tend to decrease. As the content of the rubber component and acetone insoluble matter (A) decreases, the pencil hardness tends to increase, but the impact resistance and the mold releasability during molding tend to decrease. Therefore, in this embodiment, the target pencil hardness is achieved by adjusting these to a specific range.

  The mass reduction rate at 260 ° C. of the thermoplastic resin composition according to this embodiment is preferably 1% or less, more preferably 0.9% or less, and further preferably 0.8% or less. When the mass reduction rate at 260 ° C. is 1% or less, white haze, volatile gas, and the like are suppressed, so that the appearance tends to be further improved. The mass reduction rate represents the rate of mass reduction before and after the test. The “mass reduction rate at 260 ° C.” can be measured by the method described in the examples.

  The thermoplastic resin composition according to the present embodiment has an effect that white haze is hardly generated. “White haze” refers to a phenomenon in which an entire molded product or a part of the injection molded product such as jet black appears to be cloudy. This white haze tends to occur in areas where the pressure and temperature of the resin change, etc., and may also occur in the vicinity of a corner having a small thickness and a small radius of curvature, or in the vicinity of a gate or flow end. . The cause is considered to be the orientation of the rubber component and the compatibility in the polymer alloy. Because the resin pressure is different inside the molded product, the rubber component unit exists in a spherical shape in the injection molded body, and an egg-like shape in which the spherical shape is extended. Looks different and cloudy. In the case of a polymer alloy, the compatibility of the resins varies depending on the resin temperature, so that the resin itself appears cloudy and the molded product appears cloudy. For polymer blends such as polymer alloys, the compatibility is generally indicated by a phase diagram (eg, Practical polymer alloy design 2.3 Compatibility and phase diagram).

  Since the resin composition used in the thermoplastic resin composition of the present embodiment is an LCST (Lower critical solution temperature) type, there is a critical Cloud Point. When this temperature is significantly higher than the molding temperature, stable compatibility is exhibited, but when the temperature is lower or close to the molding temperature, the compatibility becomes unstable. In the present embodiment, the present inventors have found out these causes, and found that the white haze of the molded product can be improved by combining a predetermined rubber particle size and a resin composition having a high Cloud Point.

  The thermoplastic resin composition according to the present embodiment has an effect that silver is hardly generated. “Silver” means water-, volatile matter, cracked gas in the resin, silver-white streaks that are sparkled on the surface of the resin due to the entrainment of air by screw rotation, etc. This is a phenomenon in which the appearance is impaired.

[Other additives]
The thermoplastic resin composition according to this embodiment may contain a sliding aid. The purpose of the sliding aid is to impart lubricity to the surface of automobile interior parts. The content of the sliding aid is preferably 0.05 to 2% by mass in terms of jetness and impact resistance.

  Although it does not specifically limit as a sliding adjuvant, For example, lubricants, such as aliphatic metal salt, polyolefin, polyester elastomer, polyamide elastomer, etc. are mentioned. Among these, it is preferable to include at least one or more lubricants having a fatty acid metal salt and an amide group or an ester group. By including such a sliding aid, the scratch resistance tends to be further improved.

  Although it does not specifically limit as a fatty-acid metal salt, For example, the salt of the metal and fatty acid containing 1 or more types chosen from sodium, magnesium, calcium, aluminum, and zinc is mentioned. Such a fatty acid metal salt is not particularly limited, and specifically, sodium stearate, magnesium stearate, calcium stearate, aluminum stearate (mono, di, tri), zinc stearate, sodium montanate, montan Examples include calcium acid, calcium ricinoleate, and calcium laurate. Among these, sodium stearate, magnesium stearate, calcium stearate, and zinc stearate are preferable, stearic acid-based metal salts are more preferable, and calcium stearate is more preferable. By including such a fatty acid metal salt, scratch resistance tends to be further improved.

  Although it does not specifically limit as polyolefin, For example, the composition produced | generated from at least 1 or more types, such as ethylene, propylene, an alpha olefin, is mentioned. Polyolefins also include compositions derived from the composition as a raw material. Such polyolefins are not particularly limited, and specifically, polypropylene, ethylene-propylene copolymer, polyethylene (high density, low density, linear low density), oxidized polyolefin, graft polymerized polyolefin, etc. Is mentioned. Of these, oxidized polyolefin wax and polyolefin grafted with styrene resin are preferred in terms of scratch resistance, and more preferably polypropylene wax, polyethylene wax, oxidized polypropylene wax, oxidized polyethylene wax, acrylonitrile-styrene copolymer. These are graft graft polypropylene, acrylonitrile-styrene copolymer graft polyethylene, styrene polymer graft polypropylene, and styrene polymer graft polyethylene.

  The polyester elastomer is not particularly limited. For example, a polycondensate of a dicarboxylic acid compound and a dihydroxy compound, a polycondensate of an oxycarboxylic acid compound, a ring-opening polycondensate of a lactone compound, or a mixture of these components. Examples include polyesters obtained from polycondensates and the like. Either a homopolyester or a copolyester may be used.

  The dicarboxylic acid compound is not particularly limited. For example, terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4-dicarboxylic acid, Aromatic dicarboxylic acids such as diphenoxyethanedicarboxylic acid and sodium 3-sulfoisophthalate; aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and dicyclohexyl-4,4-dicarboxylic acid; Diphenyl ether dicarboxylic acid, diphenylethane dicarboxylic acid, succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid and other aliphatic dicarboxylic acids; and mixtures of these dicarboxylic acids; these alkyl, alkoxy or halogen substituents, etc. Be mentionedThese dicarboxylic acid compounds can also be used in the form of an ester-forming derivative, for example, a lower alcohol ester such as dimethyl ester. In this embodiment, these dicarboxylic acid compounds can be used alone or in combination of two or more. Of these, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, adipic acid and dodecanedicarboxylic acid are particularly preferably used from the viewpoints of polymerizability, color tone and impact resistance.

  Although it does not specifically limit as said dihydroxy compound, For example, ethylene glycol, propylene glycol, butanediol, neopentyl glycol, butenediol, hydroquinone, resorcin, dihydroxy diphenyl ether, cyclohexane diol, hydroquinone, resorcin, dihydroxy diphenyl ether, cyclohexane diol, 2 , 2-bis (4-hydroxyphenyl) propane and the like; these polyoxyalkylene glycols and their alkyl, alkoxy or halogen-substituted products. These dihydroxy compounds can be used alone or in combination of two or more.

  Although it does not specifically limit as said oxycarboxylic acid compound, For example, oxybenzoic acid, oxynaphthoic acid, diphenylene oxycarboxylic acid etc .; These alkyl, alkoxy, and halogen substituted products are mentioned. These oxycarboxylic acid compounds can be used alone or in combination of two or more. A lactone compound such as ε-caprolactone can also be used for producing a polyester elastomer.

  The polyamide elastomer is not particularly limited, and examples thereof include an aminocarboxylic acid or lactam having 6 or more carbon atoms, or a nylon mn salt having m + n of 12 or more. The hard segment of the polyamide elastomer is not particularly limited. For example, ω-aminocaproic acid, ω-aminoenanoic acid, ω-aminocaprylic acid, ω-aminobergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, Aminocarboxylic acids such as aminododecanoic acid; lactams such as caprolactam laurolactam; nylon 6,6, nylon 6,10, nylon 6,12, nylon 11,6, nylon 11,10, nylon 12,6, nylon 11, 12, nylon 12,10, nylon 12,12 and the like.

Further, the soft segment of the polyamide elastomer is not particularly limited. For example, polyethylene glycol, poly (1,2- and 1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) Examples include polyols such as glycol, block or random copolymer of ethylene oxide and propylene oxide, and block or random copolymer of ethylene oxide and tetrahydrofuran. The number average molecular weight of these soft segments is preferably 2.0 × 10 ^{2 to} 6.0 × 10 ³ , more preferably 2.5 × 10 ^{2 to} 4.0 × 10 ³ . Note that both ends of poly (alkylene oxide) glycol may be aminated or carboxylated.

  Among these sliding aids, a combination of a stearic acid-based metal salt and a wax is particularly preferable in terms of scratch resistance. When a sliding aid is added, an acid-modified or epoxy-modified modified resin may be mixed for the purpose of improving the compatibility.

  In addition, the thermoplastic resin composition according to the present embodiment includes a phosphite compound, a hindered phenol compound, a benzotriazole compound, a benzophenone compound, a benzoate compound, and a cyanoacrylate compound as necessary. UV absorbers and antioxidants; lubricants and plasticizers such as higher fatty acids, acid ester compounds, acid amide compounds, and higher alcohols; montanic acid, salts thereof, esters thereof, half esters thereof, stearyl alcohol, stellar amide Release agents such as ethylene wax; anti-coloring agents such as phosphites and hypophosphites; nucleating agents; antistatic agents such as amine compounds, sulfonic acid compounds, and polyether compounds; 3-phenylenebis (2,6-dimethylphenyl phosphate), tetraphenyl-m May contain additives such as halogenated flame retardants; phenylene bisphosphate, phenoxyphosphoryl, phosphorus flame retardants such as phenoxyphosphazene. From the viewpoint of weather resistance, the content of these additives is preferably 0.05 to 1% by mass, respectively.

  Moreover, from the viewpoint of further improving the designability, the thermoplastic resin composition according to the present embodiment may include a known colorant. Although it does not specifically limit as a well-known colorant, For example, an inorganic pigment, an organic pigment, a metallic pigment, and dye are mentioned. Among the colorants, those in which the color of the automobile interior part is white, black, red are preferably used because they give a particularly high-class feeling to the design of the automobile interior part.

  Examples of inorganic pigments include, but are not limited to, titanium oxide, carbon black, titanium yellow, iron oxide pigments, ultramarine, cobalt blue, chromium oxide, spinel green, lead chromate pigments, cadmium pigments, and the like. .

  Examples of the organic pigment include, but are not limited to, azo pigments such as azo lake pigments, benzimidazolone pigments, diarylide pigments, and condensed azo pigments; phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; isoindolinone pigments and quinophthalone pigments Quinacridone pigments, perylene pigments, anthraquinone pigments, perinone pigments, condensed polycyclic pigments such as dioxazine violet, and the like.

  The metallic pigment is not particularly limited. For example, the metallic pigment of scaly aluminum, the spherical aluminum pigment used for improving the weld appearance, mica powder for pearl-like metallic pigment, other glass, etc. Examples include inorganic polyhedral particles coated with metal by plating or sputtering.

  Although it does not specifically limit as dye, For example, nitroso dye, nitro dye, azo dye, stilbene azo dye, ketoimine dye, triphenylmethane dye, xanthene dye, acridine dye, quinoline dye, methine / polymethine dye, thiazole dye, indamine / Indophenol dye, azine dye, oxazine dye, thiazine dye, sulfur dye, aminoketone / oxyketone dye, anthraquinone dye, indigoid dye, phthalocyanine dye and the like.

  These colorants may be used alone or in combination of two or more.

  From the viewpoint of further improving the color tone, the addition amount of these colorants is preferably 0.05 to 2% by mass, more preferably 0.1 to 1.5% by mass.

[Method for producing thermoplastic resin composition]
Although it does not specifically limit as a manufacturing method of the thermoplastic resin composition which concerns on this embodiment, For example, the method of kneading | mixing a raw material with an extruder etc. is mentioned. The kneading means is not particularly limited, and examples thereof include an open roll, an intensive mixer, an internal mixer, a kneader, a continuous kneader with a twin-screw rotor, and a mixer such as an extruder. Among these, a single screw or twin screw extruder is generally used.

  The method for supplying the raw material of the thermoplastic resin composition to the melt kneader is not particularly limited. For example, all the raw materials may be supplied to the same supply port at once, or the raw materials may be supplied from different supply ports. You may supply. For example, using an extruder having two inlets, an acetone soluble component (B) is supplied from the main inlet installed on the screw base side, and the auxiliary inlet installed between the main inlet and the tip of the extruder. Examples thereof include a method of supplying and melting and kneading a component that becomes an acetone insoluble component (A) from an inlet. Moreover, when supplying all the raw materials from the same supply port, after mixing all beforehand, you may throw into an extruder hopper and knead | mix.

  The preferred melt kneading temperature varies depending on the Vicat softening point according to ISO 306. Specifically, a temperature that is 110 to 180 ° C. higher than the Vicat softening point at the cylinder set temperature is preferable.

  Moreover, when using an extruder, it is preferable that cylinder setting temperature shall be 30-200 degreeC of supply zones, and the temperature of the kneading | mixing zone in which melt-kneading is performed shall be 110-180 degreeC higher than Vicat softening point. By setting the temperature in two stages in this way, the kneading is performed smoothly, and the appearance of the surface of the automobile interior part obtained thereafter is further improved.

  The melt kneading time is preferably about 0.5 to 5 minutes.

  Moreover, when extrusion-producing a thermoplastic resin composition, it is preferable that the volatile content in a resin composition is 1500 ppm or less at the stage of supplying to an injection molding machine. The method for adjusting the volatile content is not particularly limited. For example, the volatile content is sucked from a vent hole installed between the center of the cylinder of the twin screw extruder and the tip of the extruder at a reduced pressure of −100 to −800 hPa. It is preferable to do.

  The extruded thermoplastic resin composition can be directly cut into pellets, or formed into strands and then cut with a pelletizer to be pelletized. The shape of the pellet may be a general shape such as a cylinder, a prism, or a sphere, but a cylinder is preferable.

[Method of manufacturing automotive interior parts]
The automobile interior part according to this embodiment is made of the thermoplastic resin composition. Although it does not specifically limit as a manufacturing method of automotive interior parts, For example, injection compression molding, gas assist molding by nitrogen gas, carbon dioxide gas, etc., high-speed heat cycle molding which makes mold temperature high, etc. are mentioned. These can be used in combination. Preferred are gas assist molding, high speed heat cycle molding, and a combination of gas assist molding and high speed heat cycle molding.

  Here, “gas assist molding” is generally known injection molding using nitrogen gas or carbon dioxide gas. Gas assist molding is not particularly limited, but, for example, a method of injecting a pressurized gas into a molded body after injecting a resin into a mold cavity as disclosed in Japanese Patent Publication No. 57-14968; Japanese Patent No. 3819972 A method of injecting a pressurized gas into a cavity corresponding to one side of a molded body after injecting the resin into a mold cavity as in a gazette or the like; prefilling a thermoplastic resin with a gas as in a patent 3349070 The method of shaping | molding is mentioned. Among these, the method of press-fitting pressurized gas into the cavity corresponding to one side of the molded body is preferable.

  In the present embodiment, gas assist is preferable as the holding pressure for preventing sinking and warping. By carrying out the pressure retention for preventing sink and warp with gas assist, it becomes difficult to generate burrs even when the mold temperature is relatively high, and the pressure holding time can be shortened to prevent sink and warp.

  As the mold of the molded body, it is preferable to use a mold finished with a file of # 4000 or more, preferably # 12000 or more. The arithmetic average surface roughness Ra of the mold surface is preferably 0.02 μm or less, and more preferably 0.01 μm or less. By using such Ra molds, there is a tendency to obtain automotive interior parts having design properties such as deep jetness.

  A method for adjusting the surface of the mold to the arithmetic average surface roughness Ra is not particularly limited, and there is a method of polishing by an ultrasonic polishing machine or a manual work with a diamond file, a grindstone, a ceramic grindstone, a ruby grindstone, a GC grindstone, or the like. Can be mentioned.

  Moreover, the steel material of the metal mold to be used is preferably a quenched and tempered steel of 40 HRC or more, more preferably 50 HRC or more. Instead of polishing the mold, a chrome plated mold may be used, or a chrome plated mold may be used on the polished mold as described above.

  The mold temperature in the injection molding is preferably in the vicinity of the Vicat softening point according to ISO 306, more preferably −25 ° C. from the Vicat softening point to + 20 ° C. from the Vicat softening point, and more preferably − It is +5 degreeC from 15 degreeC-Vicat softening point. By setting it as the said mold temperature, the transcription | transfer property to the cavity surface improves more and it can obtain the automotive interior part excellent in deep jetness.

  In general, when the cavity surface temperature is increased, the time until cooling becomes longer, which causes a problem that the molding cycle becomes longer. Therefore, it is preferable to use a high-speed heat cycle molding method in which the cavity surface is heated and cooled in a short time. As a result, it is possible to achieve both improvement in sharpness and productivity. The cooling rate of the surface of the molded body that greatly affects the sharpness of the molded body is preferably 1 to 100 ° C./second, more preferably 30 to 90 ° C./second, and further preferably 40 to 80 ° C./second. It is. The cylinder set temperature in the injection molding is preferably 105 to 150 ° C. higher than the Vicat softening point according to ISO 306, and more preferably 110 to + 140 ° C. higher than the Vicat softening point.

In addition, a molding method in which the mold temperature is raised or lowered using a mold having a steam pipe or a heating wire built therein, or a molding method using supercritical CO ₂ can be preferably used.

  The temperature of the resin (the kneaded product) during injection molding is preferably molded at a temperature suitable for the resin to be molded. For example, in the case of ABS resin, rubber-modified polystyrene, and methyl methacrylate resin, a resin temperature of 220 to 260 ° C. is preferable, and in the case of a resin containing polycarbonate, a resin temperature of 260 to 300 ° C. is preferable.

  The injection speed is preferably 1 to 50 mm / s, more preferably 3 to 30 mm / s.

  The automobile interior part according to this embodiment is preferably used for a housing of an unpainted product because it has a deep jetness. Here, the “automobile interior part” is a visible design part used in the interior of an automobile. In particular, a part belonging to a non-impact area that does not require a head impact test is preferable. Specific examples of such parts include an indicator cover, a window finisher, a garnish, a molding, and various switches and covers. Moreover, the said thermoplastic resin composition can be used also in another product. Although it does not specifically limit as another product, For example, household products, daily necessities, etc. are preferable, and it is preferable to use especially as a member of the product visible to a consumer and a trader.

  Materials that can be used unpainted in automobile interior parts require design properties such as jet blackness, scratch resistance, and impact resistance, as well as high heat resistance, and are stable and beautiful without silver and white haze. Appearance is required. Such a problem has been clarified for the first time in unpainted automobile interior jet black parts, and it is difficult to obtain an injection-molded article having all such properties by conventional knowledge. However, the injection molded body according to the present embodiment can be suitably used for automobile interior parts because it has these properties.

  The shape of the automobile interior part is not particularly limited, and examples thereof include a thin shape such as a plate shape, a shape having a three-dimensional thickness, and a polygonal shape in which corners are square to a shape having many curved surfaces. It is done. Further, the size of the automobile interior part is not particularly limited, but for example, from a small shape included in a range of 10 × 10 × 10 mm to a large shape included in a range of 1,000 × 1,000 × 500. Can be mentioned.

  Hereinafter, the present embodiment will be described more specifically by way of examples. However, the present embodiment is not limited to these examples.

(1) Extraction method of acetone insolubles The content of acetone insolubles contained in the injection-molded product was confirmed by the following method. Two dried centrifuge tubes were prepared per sample, and the centrifuge tubes were allowed to cool in a desiccator for 15 minutes or more, and then precisely weighed to 0.1 mg with an electronic balance. About 1 g of a sample was cut from the injection molded body, weighed into a centrifuge tube, and precisely weighed to 0.1 mg. About 20 mL of acetone was collected with a graduated cylinder, placed in a centrifuge tube, sealed with a silicone stopper, and shaken with a shaker for 2 hours. After shaking, the sample adhering to the silicone stopper was dropped into the centrifuge tube using a small amount of acetone. Two centrifuge tubes were set diagonally to the rotor of a Hitachi high-speed cooling centrifuge, and the centrifuge was operated to perform centrifugation at a rotational speed of 20000 rpm for 60 minutes.

  After completion of the centrifugation, the sedimentation tube was removed from the rotor, and the supernatant was decanted. About 20 mL of acetone was collected with a graduated cylinder, put into a centrifuge tube, sealed with a silicone stopper, and then shaken with a shaker for 1 hour. The supernatant was decanted (after shaking for 1 hour), and about 20 mL of acetone was added again and shaken for another hour, and then the mixture was centrifuged again at 20,000 rpm for 50 minutes.

  After completion of the centrifugation, the sedimentation tube was removed from the rotor, and the supernatant was decanted. Thereafter, the same operation as the second decantation was performed once again.

  After completion of the centrifugation, about 20 mL of acetone was collected with a graduated cylinder, put into a centrifuge tube, sealed with a silicone stopper, and then centrifuged at a rotational speed of 20000 rpm for 30 minutes. After completion of the centrifugation, the sedimentation tube was removed from the rotor and the supernatant was decanted. The obtained precipitate was dried at 80 ° C. for 30 minutes and then dried at 130 ° C. for 30 minutes to obtain an acetone insoluble matter.

(1-2) Extraction method of acetone soluble part The supernatant liquid decanted in the above method was collected, and the acetone component was removed by volatilization to obtain an acetone soluble part.

(1-3) Measuring method of content of acetone insoluble matter After drying, the mixture was allowed to cool for 30 minutes or more in a desiccator. After sufficiently allowing to cool, the obtained acetone-insoluble matter was precisely weighed to 0.1 mg with an electronic balance. The content (mass%) of the acetone insoluble content relative to the total 100 mass% of the acetone insoluble content (A) and the acetone soluble content (B) was calculated by the following formula.
Acetone insoluble content (mass%) = [acetone insoluble content (g) ÷ sampled amount (g)] × 100

In the case where the injection-molded product contains an inorganic insoluble component, the content (mass percent) of the acetone insoluble component relative to the total 100 mass percent of the acetone insoluble component (A) and the acetone soluble component (B) is expressed by the following formula. Calculated.
Acetone insoluble content (mass%) = [(acetone insoluble component including inorganic insoluble content (mass%) − inorganic insoluble content (mass%)) / (100−inorganic insoluble content (mass%))] × 100
Here, “inorganic insoluble matter” refers to, for example, titanium, glass fiber, talc, calcium carbonate, etc. used for the color pigment.

(2) Mass average particle diameter of rubber component unit Acetone-insoluble matter (A) was extracted from the injection molded article, and ultrathin sections of 60 nm ± 2 nm were cut out. The ultrathin sections were stained with osminic acid and then observed with a transmission electron microscope (TEM; manufactured by Hitachi High-Technologies Corporation, product name H-600AB). The obtained TEM photograph was analyzed with image analysis software (manufactured by Asahi Kasei Engineering Co., Ltd., product name A image-kun) to obtain a mass average particle size of a rubber component unit.

(3) Content of methacrylic acid ester monomer unit Composition analysis of acetone-soluble component (B) was performed using a pyrolysis gas chromatography method, and 100 mass% of the structural unit of all resins contained in acetone-soluble component (B). The content of methyl methacrylate units relative to was calculated.

(4) Content of unsaturated nitrile monomer unit contained in graft copolymer Using acetone of Fourier transform infrared spectrophotometer (FT-IR; manufactured by PerkinElmer Japan Co., Ltd., product name Spectrum One) The composition analysis of (A) was performed, and the content of unsaturated nitrile monomer units contained in the graft copolymer with respect to 100% by mass of all grafted structural units was calculated.

(5) Graft rate (%)
The graft ratio (%) of the following graft copolymer was determined by absorption peak analysis obtained using a Fourier transform infrared spectrophotometer (FT-IR).

(6) Reduced viscosity (dl / g)
The reduced viscosity (dl / g) of the following copolymer was measured by the following method.
The thermoplastic resin is dissolved in acetone, and this is separated into an acetone-soluble component and an acetone-insoluble component by a centrifuge. The reduced specific viscosity of the non-grafted component (non-grafted component) in the thermoplastic resin in the thermoplastic resin was determined by using a solution obtained by dissolving 0.25 g of acetone-soluble component in 50 ml of 2-butanone at 30 ° C. It is obtained by measuring the outflow time in a Fenske type capillary.

(7) Weight average molecular weight of methacrylic copolymer (Mw)
The weight average molecular weight (Mw) of the methacrylic copolymer was measured by gel permeation chromatography (GPC; manufactured by Tosoh Corporation, product name HLC-8220GPC). The specific conditions were as follows: using a separation column manufactured by Tosoh Corporation (using three TSKgel-GMH _XL ), temperature 38 ° C., solvent tetrahydrofuran, sample concentration 0.1 wt / v%, sampling pitch 1 / 0.4 ( Times / sec). The molecular weight of the separated component is calculated by creating a calibration curve using the relationship between the molecular weight of TSK standard polystyrene manufactured by the company and the elution time as a cubic regression curve. The specific molecular weight content is calculated by the area ratio. The peak top molecular weight is a molecular weight corresponding to an elution time at which the peak height is maximized.

(8) Jetness (lightness (L *))
The lightness (L *) of the surface of the injection-molded product was measured according to machine condition C (de: 8 °) based on JIS Z8722. For the measurement of lightness (L *), a spectrocolorimeter “CM-2002” (manufactured by Konica Minolta) was used. Specific conditions were a light source D65, a luminous flux φ11 mm, and a visual field of 10 °. The sample was not particularly limited, but a relatively smooth portion of the injection molded product was used.

(9) Heat resistance (Vicat softening point)
It measured by B-120 method based on ISO306 using the injection molded object. The load was 50 N, and the heating rate was 120 ° C./h. The sample was about (width) 20-30 mm × (length) 20-30 mm × (thickness) 2-4 mm. In addition, when the thickness of a sample is less than 2 mm, several samples can be stacked and used.

(10) Impact resistance (Charpy impact value)
Using an injection molding machine (product name EC100S, manufactured by Toshiba Machine Co., Ltd.), a multipurpose test piece A type (ISO dumbbell test piece) with a thickness of 4 mm is formed according to ISO 294 at a cylinder temperature of 250 ° C and a mold temperature of 60 ° C. Then, after the obtained test piece was processed into a shape of 80 mm × 10 mm × 4 mm, notch processing of a predetermined size was performed according to ISO 179 and tested. As the test value, an average value of five test pieces was used.

(11) Mass reduction rate Using the pellets, the mass reduction rate was measured with TGA "MTC 1000SA" and "TG-DTA 2000SR" (manufactured by Bruker). Specifically, after drying at 90 ° C. for 4 hours to remove moisture, the temperature was raised to 260 ° C. at 100 ° C./min, and left at 260 ° C. for 30 minutes, and then the mass was measured. The weight loss rate was calculated by the following equation when the mass (m1) before the test was 100% and the mass after the test (m2).
Weight loss rate (%) = 100−m2 / m1 × 100
In addition, although there is no restriction | limiting in particular in temperature rising rate, It is preferable to heat up at 100 degrees C / min.

(12) Scratch resistance (pencil hardness)
Using an injection-molded body, measurement was performed according to JIS K5400.

(13) Appearance (white haze)
The whole injection-molded body was visually confirmed. The case where there was no unevenness or cloudiness in the color tone was evaluated as ◯, the case where it could be confirmed at a distance of 100 mm was evaluated as △, and the case where it could be confirmed at a distance of 500 mm was evaluated as x.

(14) Appearance (silver)
The surface of the injection molded body was observed at 270 ° C. The case where silver could not be confirmed was evaluated as ◯, the case where it could be confirmed at a distance of 100 mm was evaluated as △, and the case where it could be confirmed at a distance of 500 mm was evaluated as x.

(1) Raw material used (Production example 1 of graft copolymer)
In a polymerization reaction tank, polybutadiene rubber latex (mass average particle diameter measured by Microtrac Particle Size Analyzer “Nanotrac 150” manufactured by Nikkiso Co., Ltd. = 0.25 μm, solid content = 50 mass%, swelling index 40%) 110 mass Part, 0.1 part by mass of terrestrial decyl mercaptan and 25 parts by mass of deionized water were added, and the gas phase part was purged with nitrogen, followed by heating to 55 ° C. Subsequently, while the temperature was raised to 70 ° C. over 1.5 hours, a single unit consisting of 12 parts by mass of acrylonitrile, 48 parts by mass of styrene, 0.5 parts by mass of terleaded decyl mercaptan, and 0.15 parts by mass of cumene hydroperoxide. Sodium formaldehyde sulfoxylate 0.2 parts by mass, ferrous sulfate 0.004 parts by mass, ethylenediaminetetraacetic acid disodium salt 0.04 parts by mass are dissolved in a monomer mixture and deionized water 22 parts by mass. The aqueous solution was added over 4 hours. One hour after completion of the addition, the polymerization reaction was completed while controlling the polymerization reaction vessel at 70 ° C.

  To the ABS latex thus obtained, an antifoaming agent made of silicone resin (Momentive Performance Materials Japan G.K., product name TSA737, the same applies hereinafter), and a phenolic antioxidant emulsion (Chukyo Yushi Co., Ltd.) Product name L-673, the same applies hereinafter), and then solidified by adding an aqueous solution of aluminum sulfate, and after sufficient dehydration and water washing, drying is performed to obtain the graft copolymer (A-1). Obtained. At the same time, a vinyl copolymer (B-1), which is a thermoplastic resin, was also obtained. The ratios of the graft copolymer (A-1) and the vinyl copolymer (B-1) were 74.9% by mass and 25.1% by mass. Table 1 shows the results of analysis of the graft copolymer (A-1) and the vinyl copolymer (B-1).

(Production Example 2 of Graft Copolymer)
In a polymerization reaction tank, polybutadiene rubber latex (mass average particle diameter measured with a Microtrac particle size analyzer “nanotrac 150” manufactured by Nikkiso Co., Ltd. = 0.32 μm, solid content = 50 mass%, swelling index 40%) 110 mass Part, 0.1 part by mass of terrestrial decyl mercaptan and 25 parts by mass of deionized water were added, and the gas phase part was purged with nitrogen, followed by heating to 55 ° C. Subsequently, while the temperature was raised to 70 ° C. over 1.5 hours, 16.2 parts by mass of acrylonitrile, 43.8 parts by mass of styrene, 0.5 parts by mass of tertiary decyl mercaptan, 0.15 mass of cumene hydroperoxide Part of a monomer mixture and 22 parts by weight of deionized water, 0.2 parts by weight of sodium formaldehyde sulfoxylate, 0.004 parts by weight of ferrous sulfate, 0.04 parts by weight of disodium salt of ethylenediaminetetraacetate Dissolved aqueous solution was added over 4 hours. One hour after completion of the addition, the polymerization reaction was completed while controlling the polymerization reaction vessel at 70 ° C.

  After adding a silicone resin defoamer and a phenolic antioxidant emulsion to the ABS latex thus obtained, solidify by adding an aqueous aluminum sulfate solution, and after sufficient dehydration and washing with water And dried to obtain a graft copolymer (A-2). At the same time, a vinyl copolymer (B-2), which is a thermoplastic resin, was also obtained. The ratios of the graft copolymer (A-2) and the vinyl copolymer (B-2) were 75.0% by mass and 25.0% by mass. Table 1 shows the results of analysis of the graft copolymer (A-2) and the vinyl copolymer (B-2).

(Production Example 3 of Graft Copolymer)
In a polymerization reaction tank, polybutadiene rubber latex (mass average particle diameter measured with a Microtrac particle size analyzer “nanotrac 150” manufactured by Nikkiso Co., Ltd. = 0.32 μm, solid content = 50 mass%, swelling index 40%) 110 mass Part, 0.1 part by mass of terrestrial decyl mercaptan and 25 parts by mass of deionized water were added, and the gas phase part was purged with nitrogen, followed by heating to 55 ° C. Subsequently, while the temperature was raised to 70 ° C. over 1.5 hours, a single unit consisting of 18 parts by mass of acrylonitrile, 42 parts by mass of styrene, 0.5 parts by mass of terleaded decyl mercaptan, and 0.15 parts by mass of cumene hydroperoxide. Sodium formaldehyde sulfoxylate 0.2 parts by mass, ferrous sulfate 0.004 parts by mass, ethylenediaminetetraacetic acid disodium salt 0.04 parts by mass are dissolved in a monomer mixture and deionized water 22 parts by mass. The aqueous solution was added over 4 hours. One hour after completion of the addition, the polymerization reaction was completed while controlling the polymerization reaction vessel at 70 ° C.

  After adding a silicone resin defoamer and a phenolic antioxidant emulsion to the ABS latex thus obtained, solidify by adding an aqueous aluminum sulfate solution, and after sufficient dehydration and washing with water And dried to obtain a graft copolymer (A-3). Here, at the same time, a vinyl copolymer (B-3) which is a thermoplastic resin was also obtained. The ratios of the graft copolymer (A-3) and the vinyl copolymer (B-3) were 75.0% by mass and 25.0% by mass. Table 1 shows the results of analysis of the graft copolymer (A-3) and the vinyl copolymer (B-3).

(Production Example 4 of Graft Copolymer)
In a polymerization reaction tank, polybutadiene rubber latex (mass average particle diameter measured with a Microtrac particle size analyzer “nanotrac 150” manufactured by Nikkiso Co., Ltd. = 0.37 μm, solid content = 50 mass%, swelling index 40%) 110 mass Part, 0.1 part by mass of terrestrial decyl mercaptan and 25 parts by mass of deionized water were added, and the gas phase part was purged with nitrogen, followed by heating to 55 ° C. Subsequently, while the temperature was raised to 70 ° C. over 1.5 hours, a single unit consisting of 18 parts by mass of acrylonitrile, 42 parts by mass of styrene, 0.5 parts by mass of terleaded decyl mercaptan, and 0.15 parts by mass of cumene hydroperoxide. Sodium formaldehyde sulfoxylate 0.2 parts by mass, ferrous sulfate 0.004 parts by mass, ethylenediaminetetraacetic acid disodium salt 0.04 parts by mass are dissolved in a monomer mixture and deionized water 22 parts by mass. The aqueous solution was added over 4 hours. One hour after completion of the addition, the polymerization reaction was completed while controlling the polymerization reaction vessel at 70 ° C.

  After adding a silicone resin defoamer and a phenolic antioxidant emulsion to the ABS latex thus obtained, solidify by adding an aqueous aluminum sulfate solution, and after sufficient dehydration and washing with water And dried to obtain a graft copolymer (A-4). At the same time, a vinyl copolymer (B-4), which is a thermoplastic resin, was also obtained. The ratios of the graft copolymer (A-4) and the vinyl copolymer (B-4) were 74.9% by mass and 25.1% by mass. Table 1 shows the results of analysis of the graft copolymer (A-4) and the co-vinyl copolymer (B-4).

(Production example 1 of vinyl copolymer)
A mixture of 13 parts by mass of acrylonitrile, 52 parts by mass of styrene, 35 parts by mass of toluene as a solvent, and 0.05 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator was bubbled using nitrogen gas. After that, continuously using a spray nozzle in a reaction tank having an internal volume of 150 L provided with a two-stage inclined paddle type (an inclination angle of 45 degrees) stirring blade similar to that described in Example 2 of Japanese Patent No. 3664576 At a rate of 37.5 kg / hr.

  The polymerization temperature was 130 ° C., and the same amount of the reaction liquid as that of the supply liquid was continuously withdrawn so that the filling rate of the reaction liquid in the reaction tank could be maintained at 70% by volume. A jacket for temperature control was provided in a portion corresponding to the liquid phase portion of the reaction tank, and the jacket temperature was 128 ° C.

  The extracted reaction liquid was introduced into a devolatilization apparatus maintained at 250 ° C. and a high vacuum of 10 mmHg, and the unreacted monomer and organic solvent were degassed and recovered to produce a vinyl copolymer (B-5 ) Was recovered as a pellet. The results of analyzing the vinyl copolymer (B-5) are shown in Table 1.

(Production Example 2 of Vinyl Copolymer)
16 parts by mass of acrylonitrile, 49 parts by mass of styrene, 35 parts by mass of toluene as a solvent, 0.05 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator, and the temperature control jacket temperature was set to 129 ° C. Except for the above, a vinyl copolymer (B-6) was produced in the same manner as in Production Example 1 of a vinyl copolymer.

  The extracted reaction solution was introduced into a devolatilization apparatus maintained at 250 ° C. and a high vacuum of 10 mmHg, and unreacted monomer and organic solvent were degassed and recovered to produce a vinyl copolymer (B-6). ) Was recovered as a pellet. The results of analyzing the vinyl copolymer (B-6) are shown in Table 1.

(Production Example 3 of Vinyl Copolymer)
21 parts by mass of acrylonitrile, 47 parts by mass of styrene, 32 parts by mass of toluene as a solvent, 0.05 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator, and the temperature control jacket temperature was set to 128 ° C. Except for the above, a vinyl copolymer (B-7) was produced in the same manner as in Production Example 1 of a vinyl copolymer.

  The extracted reaction solution was introduced into a volatile component removing apparatus maintained at 250 ° C. and a high vacuum of 10 mmHg, and the unreacted monomer and organic solvent were degassed and recovered to produce a vinyl copolymer (B-7). ) Was recovered as a pellet. The results of analyzing the vinyl copolymer (B-7) are shown in Table 1.

(Production Example 1 of methacrylic copolymer)
2 kg of water, 65 g of tricalcium phosphate, 39 g of calcium carbonate, and 0.39 g of sodium lauryl sulfate were charged into a container having a stirrer equipped with four inclined paddle blades to obtain a mixed solution. Next, 26 kg of water was put into a 60 L reactor equipped with a stirrer equipped with three receding blades, and the temperature was raised to 80 ° C., and the mixture, 19,042 g of methyl methacrylate, 1,393 g of styrene, N-phenyl 2,787 g of maleimide, 40.64 g of lauroyl peroxide and 48.77 g of n-octyl mercaptan were added. Suspension polymerization was carried out at a temperature of about 75 ° C., and an exothermic peak was observed about 120 minutes after the raw material was charged. Thereafter, the temperature was raised to 93 ° C. at a rate of 1 ° C./min and then aged for 120 minutes to substantially complete the polymerization reaction. Next, in order to cool to 50 ° C. and dissolve the suspending agent, 20 mass% sulfuric acid was added. Next, the polymerization reaction solution is passed through a 1.68 mm mesh sieve to remove aggregates, the water is filtered off, the resulting slurry is dehydrated to obtain a bead polymer, and the resulting bead polymer is After washing with water, it was dehydrated in the same manner as above, and further washed with ion-exchanged water and repeatedly dehydrated to obtain a methacrylic copolymer (M-1). The obtained methacrylic copolymer (M-1) was a methyl methacrylate-N-phenylmaleimide-styrene copolymer. The results of analyzing the methacrylic copolymer (M-1) are shown in Table 1.

(Production Example 2 of Methacrylic Copolymer)
A methacrylic copolymer except for 18,578 g of methyl methacrylate, 1,161 g of styrene, 3,019 g of N-phenylmaleimide, 464 g of methyl acrylate, 40.32 g of lauroyl peroxide, and 47.32 g of n-octyl mercaptan. A methacrylic copolymer (M-2) was produced in the same manner as in Production Example 1 for coalescence. The obtained methacrylic copolymer (M-2) was a methyl methacrylate-methyl acrylate-N-phenylmaleimide-styrene copolymer. The results of analyzing the methacrylic copolymer (M-1) are shown in Table 1.

(Production Example 3 of Methacrylic Copolymer)
The same method as in Production Example 1 of a methacrylic copolymer except that 1,523 g of methyl methacrylate, 284 g of styrene, 163 g of maleic anhydride, 0.99 g of lauroyl peroxide, and 4.93 g of n-octyl mercaptan were used. A methacrylic copolymer (M-3) was produced. The obtained methacrylic copolymer (M-3) was a methyl methacrylate-styrene-maleic anhydride copolymer. The results of analyzing the methacrylic copolymer (M-1) are shown in Table 1.

(Production Example 4 of Methacrylic Copolymer)
A methacrylic copolymer was produced in the same manner as in Production Example 1 of a methacrylic copolymer, except that methyl methacrylate was 22,440 g, methyl acrylate 694 g, lauroyl peroxide 46.27 g, and n-octyl mercaptan 55.52 g. A polymer (M-4) was produced. The obtained methacrylic copolymer (M-4) was a methyl methacrylate-methyl acrylate copolymer. The results of analyzing the methacrylic copolymer (M-1) are shown in Table 1.

(Production Example 5 of methacrylic copolymer)
Production Example 1 of a methacrylic copolymer except that 14,482 g of methyl methacrylate, 2,758 g of styrene, 5,747 g of N-phenylmaleimide, 34.48 g of lauroyl peroxide, and 43.68 g of n-octyl mercaptan were used. A methacrylic copolymer (M-5) was produced in the same manner as above. The obtained methacrylic copolymer (M-5) was a methyl methacrylate-N-phenylmaleimide-styrene copolymer. The results of analyzing the methacrylic copolymer (M-5) are shown in Table 1.

(Other colorant example 1)
Mitsubishi Carbon Black # 850 (X-1) (trade name) (Mitsubishi Chemical Corporation carbon black, sublimation temperature 3642 ° C)

Example 1
15 parts by mass of graft copolymer (A-1), 5 parts by mass of vinyl copolymer (B-1), 15 parts by mass of vinyl copolymer (B-5), vinyl copolymer (B-6) ) 5 parts by mass, 60 parts by mass of a methacrylic copolymer, and 0.5 parts by mass of the colorant (X-1) are mixed and charged into a hopper of a twin-screw extruder (“ZSK-25” manufactured by Coperion). Then, pellets were produced at a cylinder set temperature of 250 ° C., a screw rotation speed of 200 rpm, and a discharge rate of 10 kg / hr. The pellets thus prepared were injection molded (“EC100” manufactured by Toshiba Machine Co., Ltd.) at a resin temperature of 250 ° C., a mold temperature of 70 ° C., and an injection speed of 20 mm / s to obtain a 50 mm × 90 mm × 2.5 mm flat plate injection molded body. Produced. In addition, when confirming silver, the injection molded object was produced by the method similar to flat plate production except having set the resin temperature to 270 degreeC.

(Examples 2-6, Comparative Examples 1-7)
With the composition shown in Table 2, pellets and injection molded bodies were obtained in the same manner as in Example 1.

  From the above, the thermoplastic resin composition according to the present invention has jet blackness, scratch resistance, heat resistance, and impact resistance, and gives an injection-molded article having a stable and beautiful appearance without silver or white haze. I understand.

  This application is based on a Japanese patent application (Japanese Patent Application No. 2013-233402) filed with the Japan Patent Office on November 11, 2013, the contents of which are incorporated herein by reference.

  The automotive interior parts of the present invention have jet blackness, scratch resistance, and heat resistance, have a stable and beautiful appearance without silver or white haze, and have excellent impact resistance, so painting and decoration are required. However, it is economically and environmentally useful because of its excellent design.

Claims (5)

Including acetone-insoluble matter (A) and acetone-soluble matter (B),
The content of the acetone insoluble component (A) is 5 to 18% by mass with respect to 100% by mass in total of the acetone insoluble component (A) and the acetone soluble component (B),
The acetone-insoluble component (A) contains one or more resins having different structural units, and the constituent units of all the resins contained in the acetone-insoluble component (A) have at least a mass average particle size of 0.00. 1 to 0.35 μm rubber component units, aromatic vinyl monomer units, and unsaturated nitrile monomer units are included,
The acetone insoluble matter (A) includes a graft copolymer in which at least the unsaturated nitrile monomer unit is grafted to the rubber component unit,
The content of the unsaturated nitrile monomer unit contained in the graft copolymer is 15 to 28% by mass with respect to 100% by mass of all grafted structural units,
The acetone-soluble component (B) includes one or more resins having different structural units, and the structural units of all resins included in the acetone-soluble component (B) include at least aromatic vinyl unit. A monomer unit, an unsaturated nitrile monomer unit, a methacrylate ester monomer unit, and a maleimide monomer unit,
It consists of a thermoplastic resin composition whose content of the said methacrylic acid ester monomer unit is 45-60 mass% with respect to 100 mass% of all resin structural units contained in the said acetone soluble part (B). ,
Automotive interior parts.   The automotive interior part according to claim 1, wherein the thermoplastic resin composition has a Vicat softening point in accordance with ISO 306 of 105 to 120 ° C.   The automobile interior part according to claim 1 or 2, wherein a content of the maleimide monomer unit is 5 to 13% by mass with respect to 100% by mass of the thermoplastic resin composition.   The automobile interior part according to any one of claims 1 to 3, wherein the rubber component unit includes a diene rubber unit.   In any one of Claims 1-4 whose content of the said rubber component unit is 30-60 mass% with respect to 100 mass% of all resin structural units contained in the said acetone insoluble matter (A). Automotive interior parts as described.